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Copper‐catalyzed phosphinidene transfer to ethylene, acetylene, and carbon monoxide: A computational study
Author(s) -
Amme Matthew J.,
Kazi Abul B.,
Cundari Thomas R.
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22297
Subject(s) - chemistry , phosphinidene , acetylene , exergonic reaction , ethylene , catalysis , photochemistry , carbon monoxide , electron transfer , copper , reagent , inorganic chemistry , organic chemistry
A DFT study of phosphinidene transfer by copper model catalysts is reported. PR‐transfer pathways are highly exergonic with respect to catalyst and phosphinidene transfer reagent. Calculated free energy barriers by which (dhpe)Cu(PMe) active species yields functionalized products are reasonable for modeled substrates—ethylene, acetylene, and carbon monoxide. Calculations suggest a (dhpe)Cu I (‐PMe· − ) formulation as more appropriate than (dhpe)Cu II (=PMe 2− ). The preferred pathway for production of phosphirane (phosphirene) is via direct [1 + 2] addition of ethylene (acetylene) to the PMe group of (dhpe)Cu(PMe), which contrasts the [2 + 2] mechanism for the reaction of ethylene with Ni 0 ‐phosphinidenes. In light of simulations for neutral and cationic models, it is concluded that the extra electron in copper destabilizes [2 + 2] pathways. Calculated energetics for (dhpe)Cu(PMe) versus (en)Cu(PMe), dhpe = 1,2‐ bis (dihydrophosphino)ethane, en = ethylenediamine, indicate that the former is a more potent for PR‐transfer. Thus, it is inferred that modifications that result in a more electron deficient metal center will yield better group transfer catalysts. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010